(E)-1-[(4-methoxyphenyl)methoxy]-3-methylpent-2-en-4-yne | 174416-86-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-1-[(4-methoxyphenyl)methoxy]-3-methylpent-2-en-4-yne
• 英文别名: 1-methoxy-4-({[(E)-3-methylpent-2-en-4-yn-1-yl]oxy}methyl)benzene；(E)-1-methoxy-4-((3-methylpent-2-en-4-ynyloxy)methyl)benzene；1-methoxy-4-[[(E)-3-methylpent-2-en-4-ynoxy]methyl]benzene
• CAS: 174416-86-5
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: GXYCRUQKZASZDT-FMIVXFBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1-[(4-methoxyphenyl)methoxy]-3-methylpent-2-en-4-yne 在 二氯二茂锆 、 二异丁基氢化铝 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 0.83h， 以72%的产率得到(E,E)-1-iodo-5-[(4-methoxyphenyl)methoxy]-3-methylpenta-1,3-diene
  参考文献：
  名称：

  苯酚内酯核心二萜化合物 6 的全合成：合成具有异环的反式反顺式连接的外消旋十氢苯并环丁异苯并呋喃

  摘要：

  描述了对“酚醛酸内酯核心二萜 6”(5) 的合成努力。它包含环己醇（A 环）、环己烷（B 环）和环己烯（C 环），它们分别呈反式和顺式成环。使它们独特的是 A 和 C 环之间的反（或“反”）关系。在新型环己酮环化中建立了反式配置的 A/B 环结。当尝试与不同电子需求的二烯进行分子内 Diels-Alder 反应时，C 环的反选择性顺式环化失败 (21, 31)。相比之下，基于分子内 [2+2]-光环加成的 C 环前体的反选择性顺式环化成功。它以70%的产率提供了四环38。它包含一个密集功能化的 4 元环。它应该适合开环和/或重排。因此，化合物38应该可用于在未来的工作中进行目标结构5。

  DOI：

  10.1002/ejoc.201700198
• 作为产物：
  描述：

  (E)-(5-(4-methoxybenzyloxy)-3-methylpent-3-en-1-ynyl)trimethylsilane 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 反应 1.5h， 以88%的产率得到(E)-1-[(4-methoxyphenyl)methoxy]-3-methylpent-2-en-4-yne
  参考文献：
  名称：

  Relative Stereochemical Determination and Synthesis of the C1−C17 Fragment of a New Natural Polyketide

  摘要：

  The challenging determination of the relative stereochemistry of a complex natural polyketide portion was achieved. After careful NMR analysis, a concise synthesis of a set of possible relative diastereomers (only 6 diastereomers out of the 32 initially envisioned) has been carried out using a common strategy based on enantioselective aldol reactions. With a high predictability, final NMR comparison established the relative stereochemistry of the C1-C17 fragment of this natural product.

  DOI：

  10.1021/jo9012833

文献信息

• Enantioselective Synthesis of Chromans for the Preparation of Enantiopure Vitamin E and Analogues
  作者：Lutz F. Tietze、Jochen Görlitzer

  DOI：10.1055/s-1997-1278

  日期：1997.8

  Coupling of the different protected (hydroxymethyl)enynes 11a-e and 12a-c with the iodoarene 7 in the presence of catalytic amounts of Pd(PPh3)4 afforded the arylenynes 5a-e and 6a-c which were transformed into the monoprotected chiral trihydroxy compounds 13a-d and 14a,b by Sharpless bishydroxylation with >95% ee for 13a-d, 91% ee for 14b and 64% ee for 14a. A 5-step transformation of 13a led to the desired chroman derivative 3a which was cleaved to give the aldehyde 2 a known precursor for the enantioselective synthesis of vitamin E.

  不同保护形式的（羟甲基）烯炔 11a-e 和 12a-c 在催化量的 Pd(PPh3)4 存在下与碘芳烃 7 发生偶联反应，得到了芳烯炔 5a-e 和 6a-c，这些化合物通过 Sharpless 双羟基化转化为单保护的手性三羟基化合物 13a-d 和 14a,b，其中 13a-d 的较高对映体过量达到 >95%，14b 的对映体过量为 91%，14a 的对映体过量为 64%。对 13a 进行 5 步转化，得到了所需的 chroman 衍生物 3a，该化合物经过裂解生成醛 2，这是一种已知的维生素 E 选择性合成的前体。
• Toward the Development of a General Chiral Auxiliary. A Total Synthesis of (+)-Tetronolide via a Tandem Ketene-Trapping [4 + 2] Cycloaddition Strategy
  作者：Robert K. Boeckman,、Pengcheng Shao、Stephen T. Wrobleski、Debra J. Boehmler、Geoffrey R. Heintzelman、Antonio. J. Barbosa

  DOI：10.1021/ja0581346

  日期：2006.8.1

  A highly convergent, enantioselective total synthesis of the aglycone of the tetrocarcins, (+)-tetronolide, is described. The synthesis highlights the use of several new methods, including camphor auxiliary-directed asymmetric alkylation and the enantioselective preparation of acyclic mixed acetals bearing chirality at the acetal center, and the highly efficient connection of the two major precursors

  描述了 tetrocarcins 的苷元 (+)-tetronolide 的高度收敛、对映选择性全合成。该合成强调了几种新方法的使用，包括樟脑辅助导向的不对称烷基化和在缩醛中心具有手性的无环混合缩醛的对映选择性制备，以及两种主要前体通过乙烯酮捕获/分子内的高效连接。 4 + 2] 环加成策略。
• Highly Selective DNA Alkylation at the 5‘ Side G of a 5‘GG3‘ Sequence by an Aglycon Model of Pluramycin Antibiotics through Preferential Intercalation into the GG Step
  作者：Kazuhiko Nakatani、Akimitsu Okamoto、Takahiro Matsuno、Isao Saito

  DOI：10.1021/ja980801q

  日期：1998.11.1

  Altromycin B and kapurimycin Ag are new members of the pluramycin family antibiotics that alkylate N7 of guanine (G) in duplex DNA at an epoxide subunit attached to the C2 position of the pyranone ring. While 5'AG3' selective alkylation by altromycin B was accounted for by selective binding to the sequence, it remained uncertain why kapurimycin A(3), which is structurally similar to an aglycon part of altromycin B but has an epoxide subunit with an opposite absolute configuration, selectively alkylates 5' G of the 5'GG3' sequence. To clarify the molecular basis for the sequence-selective G alkylation by kapurimycin A(3), we have examined the DNA cleavage sequence selectivity of an enantiomeric pair of an aglycon model of pluramycin antibiotics and calculated total energy change upon intercalation of the model into a specific sequence by means of the DFT-HF hybrid method at the B3LYP/6-31G(d) level. Only an enantiomer with the same epoxide absolute configuration as that of kapurimycin Ag showed a remarkable G alkylation reactivity with a high selectivity for 5' G of the 5'GG3' sequence, Molecular mechanics calculations suggested that the intercalation of the aglycon model in an orientation perpendicular to neighboring base pairs is essential for the effective G alkylation at 5' G of GN sequences, and the efficiency for G alkylation is not dependent upon the sequence being intercalated. DFT-HF hybrid calculations suggested that the intercalation of the model is energetically most favorable into GG step. These results suggested that highly 5' G selective alkylation of the GG sequence by kapurimycin A(3) arises from a selective intercalation into the GG step. Stacking interaction with both 5' and 3' side Gs is a basis for the stabilization of the intercalated complex.
• Synthesis of an ABC Ring Analogue of Kapurimycin A3 as an Effective DNA Alkylating Agent
  作者：Kazuhiko Nakatani、Akimitsu Okamoto、Isao Saito

  DOI：10.1002/anie.199727941

  日期：1997.1.7
• Relative Stereochemical Determination and Synthesis of the C1−C17 Fragment of a New Natural Polyketide
  作者：Etienne Fleury、Marie-Isabelle Lannou、Olivia Bistri、François Sautel、Georges Massiot、Ange Pancrazi、Janick Ardisson

  DOI：10.1021/jo9012833

  日期：2009.9.18

  The challenging determination of the relative stereochemistry of a complex natural polyketide portion was achieved. After careful NMR analysis, a concise synthesis of a set of possible relative diastereomers (only 6 diastereomers out of the 32 initially envisioned) has been carried out using a common strategy based on enantioselective aldol reactions. With a high predictability, final NMR comparison established the relative stereochemistry of the C1-C17 fragment of this natural product.